School of Food and Biological Engineering, Engineering Research Center of Bio-process, Ministry of Education, Hefei University of Technology, Hefei, China.
Analyst. 2019 Apr 8;144(8):2765-2772. doi: 10.1039/c9an00132h.
Fluorescent gold nanoclusters (Au NCs) are new emerging fluorescent nanomaterials with broad application prospects but limited by the complicated preparation, low quantum yield (QY) and poor biological applications. Here we develop a one pot etching approach for synthesizing fluorescent Au NCs by using the common citrate-capped gold nanoparticles (Au NPs) as the precursor and the poly(amidoamine) (PAMAM) dendrimer as the etching and templating agent. The synthesis conditions are optimized and products are characterized in detail. The results confirm that we have successfully synthesized PAMAM-templated Au NCs (Au-PAMAM NCs) with strong blue emission at 453 nm and a high fluorescence QY of 18%. The optical properties are remarkably superior to that of most other reported fluorescent Au NCs since the formed specific cross-linking structures of Au-PAMAM NCs rigidify the surface Au(i)-ligands and enhance the inner aurophilic interactions. Interestingly, Au-PAMAM NCs display a sensitive and selective fluorescence response toward temperature and Cr2O72- ions, respectively. Quantitative analysis reveals the excellent capacity to distinguish temperature in the range of 15 °C-80 °C and to sense Cr2O72- in a linear range of 0-55 μM with a detection limit of 1.9 μM. Experiments evidence that there is no interference when sensing each of these targets, making Au-PAMAM NCs potential fluorescent probes for these two targets. By means of the small size, excellent water solubility, negligible cytotoxicity, and great cell penetration ability, Au-PAMAM NCs are successfully applied to monitor the dynamic change of temperature and Cr2O72- ions in living cells. This study paves the way for synthesizing high emission and highly biocompatible Au NCs with promising potential in biosensing and imaging in the future.
荧光金纳米团簇(Au NCs)是一种新兴的荧光纳米材料,具有广阔的应用前景,但由于其制备复杂、量子产率(QY)低以及生物应用受限。在这里,我们开发了一种一锅法,使用常见的柠檬酸封端的金纳米粒子(Au NPs)作为前体,聚(酰胺-胺)(PAMAM)树枝状大分子作为蚀刻和模板剂来合成荧光 Au NCs。优化了合成条件,并详细表征了产物。结果证实,我们成功地合成了具有强蓝色发射(453nm)和高荧光QY(18%)的 PAMAM 模板 Au NCs(Au-PAMAM NCs)。由于形成的特定交联结构使 Au-PAMAM NCs 的表面 Au(i)-配体刚性化并增强了内部金键相互作用,因此其光学性质明显优于大多数其他报道的荧光 Au NCs。有趣的是,Au-PAMAM NCs 对温度和 Cr2O72-离子分别表现出敏感和选择性的荧光响应。定量分析表明,其在 15°C-80°C 范围内具有出色的温度区分能力,并且能够线性感应 0-55μM 范围内的 Cr2O72-,检测限为 1.9μM。实验证明,在感应这些目标物时,彼此之间没有干扰,这使得 Au-PAMAM NCs 成为这两种目标物的潜在荧光探针。由于具有尺寸小、水溶性好、细胞毒性小和穿透能力强等优点,Au-PAMAM NCs 成功地应用于监测活细胞中温度和 Cr2O72-离子的动态变化。本研究为合成具有高发射率和高度生物相容性的 Au NCs 铺平了道路,为未来在生物传感和成像方面具有广阔的应用前景。